JP2648917B2 - Processing method of silver halide color photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material. In particular, the present invention relates to a method for continuously operating while greatly reducing the amount of water (for example, the amount of washing water). The present invention also relates to a processing method in which no turbidity or mold due to bacteria is generated in a washing bath or a stabilizing bath, and the processed photographic material has excellent preservability.

(Prior Art) In a silver halide color photographic light-sensitive material based on the principle of color-reducing three primary colors, a blue-sensitive silver halide emulsion layer containing a coupler that forms a yellow dye by coupling with an oxidized aromatic primary amino developer is used. A green-sensitive silver halide emulsion layer containing a coupler forming a magenta dye, and a red-sensitive silver halide emulsion layer containing a coupler forming a cyan dye, and an intermediate layer for preventing color mixing between the respective emulsion layers. And a non-photosensitive layer such as a protective layer for preventing direct contact between the emulsion layer and the foreign matter. To each of these emulsion layers and non-photosensitive layers, the above-mentioned couplers, color mixture inhibitors, color fading inhibitors, ultraviolet absorbers, etc. are added according to the purpose. These various additives are hydrophobic substances and are often dissolved in a high-boiling organic solvent and added in an emulsified state.

It is generally known that the amount of coated silver can be reduced by making the color coupler used in a color photographic light-sensitive material 2 equivalents. The use of a two-equivalent coupler can improve the desilvering property and the recoloring failure during the development processing, and is therefore preferable in terms of speeding up the processing and obtaining good photographic images. THJames has already described these two-equivalent couplers.
Written by The Theory of the Photographic Process (Macmilla
n, Forfh Edition), pages 354-361.

Up to now, the equivalent of each of the yellow, magenta and cyan couplers has been reduced to two equivalents. Among them, the magenta coupler has a great advantage that, when the photographic material is processed, the stain is not increased when the processed photographic material is stored for a long time in a dark place.

However, when a silver halide color light-sensitive material containing a 2-equivalent magenta coupler is subjected to conventional processing methods such as color development, bleach-fixing, and washing with water, color fading and light stain of the obtained color photographic image become large. Many cases have occurred.

In general, the standard processing steps of a silver halide color light-sensitive material include color development for forming a color image, desilvering for removing developed silver and undeveloped silver, and washing and / or image stabilization. . Recently, processing time has been shortened due to requests for shortened finish delivery time, reduction of work in the lab, or miniaturization and simplified operation of a processing system for a small lab called a so-called mini lab. In response to demands for cost reductions such as water saving and energy saving, low replenishment of washing water is being performed.

Both the shortening of the washing step and the stabilization step and the reduction in replenishment have been serious problems in practical use because the above-mentioned photobleaching and light stain are further increased in the processing of a photosensitive material containing a 2-equivalent magenta coupler. In addition, low replenishment increases the residence time of the washing water and stabilizing solution in the automatic developing machine, so that bacteria and fungi grow in the solution and stains the processed photosensitive material. Problems arise.

Some attempts have been made to improve the photobleaching of a light-sensitive material containing a 2-equivalent magenta coupler. For example, JP-A-61-4050, JP-A-61-4052, and JP-A-61-4054 disclose a method of improving photobleaching by adding a bactericide, a sulfite, an iron compound, and the like to a stabilizing solution. It is noted.

However, when these methods were tried, almost no effect was observed, and at least no practical effect was expected.

On the other hand, as a method for suppressing the growth of microorganisms in the washing water and the stabilizing solution, there is an addition of an antibacterial agent. Isothiazolone compounds are known as particularly effective antibacterial agents. For example, JP-A-57-8542 discloses a method in which an isothiazolone-based antibacterial agent (a deterrent agent) and a benzoisothiazolone-based antibacterial agent (a deterrent agent) are added to a washing bath. Although such an antibacterial agent is effective in solving the above problem, it is heated in the drying step following the water washing step, so it may volatilize and impair the safety of the working environment, and requires extra investment such as installation of an exhaust device. Is required. Further, the use of an antibacterial agent has a disadvantage such that the processed color light-sensitive material becomes sticky and easily adheres, and the above problem has not yet been sufficiently solved.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a processing method which does not deteriorate the image storability of a processed photosensitive material even if the amount of washing water is largely reduced. . It is a second object of the present invention to provide a processing method that does not generate stains due to the growth of bacteria and fungi in a washing tank or a stabilizing tank.

(Means for Solving the Problems) The object of the present invention has been achieved by the following methods.

That is, in a silver halide color light-sensitive material containing at least one magenta coupler represented by the following general formula (I) or (II), the concentrations of calcium and magnesium compounds are reduced to 5 mg / m or less as calcium and magnesium, respectively. Unused washing replenisher and / or
Alternatively, it has been achieved by treating an unused stable replenisher while replenishing it with a washing bath and / or a stabilizing bath.

General formula (I) General formula (II) In the formula, R ₁ and R ₃ represent a phenyl group, R ₂ is a hydrogen atom,
Represents an aromatic acyl group or an aliphatic or aromatic sulfonyl group, R ₄ represents a hydrogen atom or a substituent,
X ₁ and X ₂ each represent a group capable of leaving during the coupling reaction with the oxidized form of the developing agent, and Za and Zb represent Or = N-. R ₀ represents a hydrogen atom or a substituent.

The couplers of the general formulas (I) and (II) are known two-equivalent magenta couplers. Although light-sensitive materials containing these couplers are excellent in color developability, color reproducibility, dark preservability, etc., practically, there are many problems of fading magenta dyes and increasing stains due to light irradiation. In particular, when a water-saving treatment is performed in a step having an action of washing out each processing liquid component in a step of washing, stabilizing liquid, that is, development, bleaching and fixing,
Since the prebath, especially the bleaching and fixing components, remain in the processed photographic material more, the above-mentioned problem becomes remarkable. Further, the same problem occurs when the processing time of the water washing and stabilization step is short, and this is most noticeable when the processing time of the water washing and the stabilization step is short in water saving processing.

The present inventors have analyzed this problem and have conducted intensive studies. As a result, one of the major problems is that calcium and magnesium ions coexist with bleaching and fixing solution components in the processed photographic material. He found that. Normally, tap water and well water are used as the washing water and the preparation liquid of the stabilizing solution, and therefore these contain a considerable amount of calcium and magnesium, which is the cause.

Therefore, the above problem could be solved by reducing the calcium and magnesium in the washing water and the stabilizing solution.

The effect of the present invention becomes more significant as the replenishment amount of the washing water and the stabilizing solution is smaller in the case of continuous processing in an automatic developing machine. The effect appears when the ratio of the replenishment amount to the amount brought into the washing or stabilization process from the pre-bath by the photosensitive material is 50 times or less, and 30
When it is less than twice, it becomes more remarkable, and it is preferable from the viewpoint of water saving. Even in the case where washing and stabilization are performed with stored water instead of continuous replenishment, the use of the present invention is effective because the frequency of washing and stabilizing liquid exchange can be reduced. In the case of continuous or intermittent replenishment, the amount is preferably 0.5 to 50 times, more preferably 2 to 30 times. The replenishment amount of the washing water or the stabilizing solution is preferably 1 / m ² or less, more preferably 5 / m ² or less.
A 00ml / m ^2.

Similarly, when the processing time of the washing and stabilization steps is short, the effect becomes more remarkable, which is preferable from the viewpoint of rapid processing. As a preferred treatment time, the total time of the water washing and / or stabilization step is 2 minutes or less, more preferably 1 minute.
Minutes or less.

In the present invention, the washing and stabilizing steps are preferably performed in a multistage countercurrent system from the viewpoint of saving water. A particularly preferred number of stages is 2 to 4.

In the present invention, washing is a process for securing performance after processing by washing out processing solution components adhering to or occluded in the color photosensitive material and components of the photosensitive material that are no longer required during the processing. It is.

The stabilizing solution refers to a solution to which a compound that imparts an image stabilizing effect, which cannot be obtained by merely washing with water as described above, is added, and examples thereof include an example containing formalin as an image stabilizer.

The present invention reduces the concentration of calcium and magnesium compounds in an unused replenisher to be replenished to the washing step and / or the stabilizing step by 5 m each as magnesium and calcium.
It can be achieved by reducing it to g / or less. Therefore, the unused replenisher for the washing step and / or the stabilizing step in the present invention preferably has a calcium and magnesium concentration of 5 mg / or less, respectively, more preferably
The dose is 3 mg / or less, more preferably 1 mg / or less.

The calcium and magnesium in the unused replenisher in the washing step and / or the stabilizing step can be reduced by various known methods as described above. The content of calcium and magnesium compounds can be reduced, for example, by means of ion exchange resins, zeolites or reverse osmosis devices.

Various cation exchange resins can be used as the ion exchange resin, but it is preferable to use a Na type cation exchange resin in which Ca and Mg are replaced with Na. Also, an H-type cation exchange resin can be used, but in this case, the pH of the treated water becomes acidic. Therefore, in order to avoid this, it is preferable to use it together with an OH-type anion exchange resin.

Aminocarboxylic acid type chelate resins can also be used as one type of cation exchange resin.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such an ion exchange resin include, for example, Diaion SK-1B or Diaion PK-216 (trade name, manufactured by Mitsubishi Chemical Corporation).
And the like. The substrate of these ion exchange resins preferably has a charge amount of divinylbenzene of 4 to 16% based on the charge amount of all monomers at the time of production. As the anion exchange resin that can be used in combination with the H-type cation exchange resin, a strongly basic anion exchange resin having a styrene-divinylbenzene copolymer as a base and having a tertiary amine or quaternary ammonium group as an exchange group is preferable. .
Examples of such anion exchange resins include, for example, Diaion SA-10A or Diaion PA-418, also manufactured by Mitsubishi Kasei Corporation.

Any known method can be used to remove calcium and magnesium in the replenisher using these ion exchange resins, but it is preferable to pass water through a column filled with the ion exchange resin. . The speed at which water is passed is 1 to 100 times, preferably 5 to 50 times, the resin volume per hour.

Zeolite is an insoluble aluminum silicate
(AlO ₂ ) _x · (SiO ₂ ) _y · Z (H ₂ O). In the general formula, any of A-type zeolites in which x and y are equal and X-type zeolites in which x and y are different can be used in the present invention. In particular, X-type zeolites are excellent in exchange ability for both calcium and magnesium. preferable. As an example of such a zeolite, there can be mentioned a molecular sieve LINDE ZB-300 manufactured by Union Carbide. Zeolites are available in various particle sizes, but when packed in a column and brought into contact with water, particles larger than 30 mesh are suitable.

As the reverse osmosis treatment device used in the present invention, a known device can be used without limitation, but the area of the reverse osmosis membrane is 3 m.
^It is desirable to use an ultra-compact device with a pressure of ² or less and a working pressure of 30 kg / m ² or less, particularly preferably 2 m ² or less and 20 kg / m ² or less. When such a small device is used, workability is good and a sufficient water saving effect can be obtained. Further, activated carbon or a magnetic field can be passed.

As the reverse osmosis membrane included in the reverse osmosis treatment device, a cellulose acetate membrane, an ethylcellulose / polyacrylic acid membrane, a polyacrylonitrile membrane, a polyvinylene carbonate membrane, a polyether sulfone membrane, or the like can be used.

Further, the liquid sending pressure is usually 5 to 60 kg / cm ^2, but in order to achieve the object of the present invention, 30 kg / cm ² or less is sufficient,
What is called a low-pressure reverse osmosis device of 10 kg / cm ² or less can be sufficiently used.

As the structure of the reverse osmosis membrane, any of a spiral type, a tumbler type, a hollow fiber type, a pleated type, and a rod type can be used.

In the present invention, the unused replenisher replenished in the washing step and / or the stabilizing step (hereinafter, referred to as a washing replenisher and a stable replenisher) is preferably sterilized before use. Specific methods of sterilization treatment include the addition of a bactericide,
Excessive heating with a filter with a pore size of 0.8 microns or less,
Although irradiation with ultraviolet rays may be mentioned, it is preferable to use a bactericide from the viewpoint of certainty of the effect. Such bactericides include hypochlorous acid, dichloroisocyanuric acid,
Active halogen releasing compounds such as trichloroisocyanuric acid and salts thereof, isothiazolone compounds such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1 , 2
-Benzoisothiazolone compounds represented by -benzoisothiazolin-3-one; triazole compounds such as benzotriazole; silver ion releasing compounds such as silver nitrate and silver oxide; sulfanilamide; 10,10'-oxybisphenoxyarsine And Hiroshi Horiguchi, "The Chemistry of Bactericidal and Antifungal Agents", Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
Can be used. These fungicides can be used in the range of 1 to 1000 mg /, but preferably 1 to 1000 mg /.
It is used in the range of -100 mg /, particularly preferably 3-30 mg /.

Above all, its effects, less influence on photosensitive materials,
From the viewpoint of ease of use and the like, an active halogen releasing compound is preferable in the replenisher for washing with water, and an isothiazolone compound is preferable in the replenisher for stable washing.

The washing bath and / or the stabilizing bath of the present invention may contain a chelating agent having calcium and magnesium and a stability constant of 6 or more.

Here, the stability constant (K _MA ) refers to a value represented by the following equation.

Here, [MA] is the molar concentration of the metal chelate, [M] is the molar concentration of the metal ion, and [A] is the molar concentration of the chelating agent anion.

Chelating agents having such stability constants are described in “Metal Chelate III” by Keihei Ueno (published by Nankodo), “Dotite Reagents Comprehensive Catalogue 13th Edition” published by Dojindo Laboratories, and Shiren (LGSillen et al.) It can be easily selected from the chelate compounds described in "Stability Constant of Metal Complex" (published by 1964 Chemical Society).

Among these chelating agents, the following are specifically exemplified.

The compound is used in an amount of 3 × 10 ^{-4 to} 3 × 10 ^-2 mol /, preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol /.

Such a chelating agent has an effect of further enhancing the effects of the present invention.

PH in each washing bath constituting the washing step in the present invention
Is 5 to 9, preferably 6 to 8. The pH of the washing replenisher supplied to these baths is in the range of 4 to 9, preferably 5 to 8. The processing temperature is 20-40
° C, preferably 30 to 40 ° C.

On the other hand, in the present invention, a compound having an effect of stabilizing an image is added to the stabilizing bath.Specifically, formaldehyde, acetaldehyde, propionaldehyde, glutaraldehyde for the purpose of inactivating the residual coupler, Formaldehyde sodium bisulfite adduct,
Aldehyde compounds such as glutaraldehyde sodium bisulfite adduct, acetic acid, boric acid, phosphoric acid, citric acid, tartaric acid and salts thereof, and aminopolycarboxylic acids and aminopolyphosphonic acids for the purpose of adjusting the membrane surface pH after treatment , Alkylidene diphosphonic acid, chelating agents such as phosphonocarboxylic acid and salts thereof, ammonium chloride, ammonium nitrate,
Various ammonium salts such as ammonium sulfate and ammonium phosphate are added in an amount and in a form to exert the respective effects.

The pH of each stabilizing bath constituting the stabilizing step is from 4 to 9, preferably from 4.5 to 6.5. The pH of the stable replenisher supplied to these baths is 4-9, preferably 4-7.

The processing temperature in the stabilizing step is 20 to 40 ° C, preferably 30 to 40 ° C. Further, when the washing step and / or the stabilizing step follows the fixing or bleach-fixing step, part or all of the overflow discharged from the washing step and / or the stabilizing step with replenishment is fixed or bleach-fixed. Preferably.

In addition to the above, when the washing step or the stabilizing step of the present invention is the final step of the treatment, a surfactant is added to obtain uniform drying. Also, a fluorescent whitening agent and a hardening agent can be added.

The present invention can be widely applied to the processing of silver halide color photographic light-sensitive materials. In particular, the processing of silver halide color photographic light-sensitive materials such as color paper, color negative film, reversal color paper, reversal color film, direct positive paper, etc. It is preferably applied to color paper.

In the processing method of the present invention, when the water washing or stabilization processing is used after the processing having the fixing ability, the above-mentioned problem can be further solved. Examples of applications to various processes for color photographic light-sensitive materials include the following.

A. Color development-bleach-fix-wash-dry B. B -wash-bleach-fix-wash-dry C. 〃 -bleach-fix-wash-dry D. 〃 -bleach-bleach-fix-fix-wash-dry Color development-bleach-bleach-fix-rinse-dry F .. -Fix-bleach-fix-rinse-dry G.〃 -Bleach-rinse-fix-stable-dry H.〃 -Bleach-fix-stable-dry I.〃 -Bleaching-Bleaching-Stable-Dry J ..- Bleaching-Stable-Dry K.〃-Fixing-Bleaching-Stable-Dry In the above G to H, a washing step is provided before the stabilizing step. There is also.

 Hereinafter, the treatment bath will be described.

Color development The color developer used in the development of the photosensitive material of the present invention is:
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as this color developing agent, but p-
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates thereof,
Hydrochloride, phosphate or p-toluenesulfonate,
Tetraphenylborate, p- (t-octyl) benzenesulfonate and the like can be mentioned. These diamines are generally more stable in a salt than in a free state, and are preferably used.

Examples of the aminophenol-based derivatives include o-aminophenol, p-aminophenol, and 4-amino-2.
-Methylphenol, 2-amino-3-methylphenol, 3-oxy-3-amino-1,4-dimethylbenzene and the like.

In addition, Photographic Processing Chemistry by LFA Meson, Focal Press (1966)
Year) (LFAMason, “Photographic Processing Chemis
try ", Focal Press) at pages 226-229, U.S. Patent 2,193,015.
No. 2,592,364 and JP-A-48-64933 may be used. If necessary, two or more color developing agents can be used in combination.

The color developing solution is a pH buffer such as an alkali metal carbonate, borate or phosphate; a development inhibitor or an antifoggant such as bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds. Hydroxylamine, diethylhydroxylamine, triethanolamine, compounds described in German Patent Application (OLS) No. 2622950, preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene Development accelerators such as glycols, quaternary ammonium salts, amines, thiocyanates, 3,6-thiaoctane-1,8-diol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; An auxiliary developing agent such as phenyl-3-pyrazolidone; a viscosity-imparting agent; Njiamin tetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N- hydroxymethyl diamine triacetic acid,
Diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids represented by the compounds described in JP-A-58-195845, 1-hydroxyethylidene-1,1'-diphosphonic acid, Research Disclosure 18170 (May 1979) described organic phosphonic acid,
Aminophosphonic acids such as aminotris (methylenephosphonic acid) and ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, JP-A-52-102726, and Research Disclosure 18170 (May 1979) Chelating agents such as the phosphonocarboxylic acids described in (Mon.).

In general, the color developing agent is used in an amount of about 0.1 per color developing solution.
It is used at a concentration of 1 g to about 30 g, more preferably about 1 g to about 15 g per color developing solution. Further, the pH of the color developing solution is usually 7 or more, and most usually from about 9 to about 13
Used in Further, the color developing solution can be reduced by using a replenishing solution in which the concentration of a halide, a color developing agent or the like is adjusted.

In the present invention, it is preferable that the above-mentioned benzyl alcohol is not substantially contained as a development accelerator.

The term "substantially not contained" as used herein means that the color developer 1
2 ml or less, preferably 0.5 ml or less, and more preferably not contain at all. When benzyl alcohol is not contained, the present invention exerts a better effect.

The processing temperature of the color developer of the present invention is preferably from 20 to 50C, more preferably from 30 to 40C. Processing time is 20 seconds ~
It is 10 minutes, more preferably 30 seconds to 5 minutes.

Bleaching Solution, Bleach-Fixing Solution, Fixing Solution As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, a ferric ion complex is composed of ferric ion and aminopolycarboxylic acid, aminopolyphosphonic acid or a mixture thereof. Complex with a chelating agent such as a salt of Aminopolycarboxylate or aminopolyphosphonate is a salt of aminopolycarboxylic acid or aminopolyphosphonic acid with an alkali metal, ammonium or a water-soluble amine. Alkali metals include sodium, potassium, lithium and the like, and water-soluble amines include methylamine, diethylamine, triethylamine, alkylamines such as butylamine, finger cyclic amines such as cyclohexylamine, aniline, arylamines such as m-toluidine, and Heterocyclic amines such as pyridine, morpholine and piperidine.

Representative examples of such chelating agents such as aminopolycarboxylic acids and aminopolyphosphonic acids or salts thereof include ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid 1,3-diaminolopanetetraacetic acid cyclohexanediaminetetraacetic acid iminodiacetic acid glycoletherdiaminetetraacetic acid Acetic acid and salts thereof such as Na, NH ₃ and the like can be mentioned, but are not limited to these exemplified compounds.

The ferric ion complex salt may be used in the form of a complex salt or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate,
Complex salts which may form ferric ion complex salts in solution using ferric ammonium sulfate, ferric phosphate and the like and chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid and phosphonocarboxylic acid When using in the form of
One kind of complex salt may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one type of ferric salt is used. Alternatively, two or more types may be used. Further, one or more chelating agents may be used. In any case, the chelating agent may be used in excess of the amount of forming the ferric ion complex salt. Of the iron complexes, iron aminopolycarboxylate iron complexes are preferable, and the amount of addition is 0.1 to 1 mol /, preferably 0.2 to 0.4 mol / in a bleaching solution of a color photographic light-sensitive material for photography such as a color negative film. In the bleach-fix solution, 0.05 to 0.5 mol /, preferably
0.1 to 0.3 mol /. In a bleaching solution or a bleach-fixing solution of a color photographic light-sensitive material for printing such as color paper, the amount is 0.03 to 0.3 mol /, preferably 0.05 to 0.2 mol /.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
No. 1,290,812, JP-A-53-95630, compounds having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July, 1978), and JP-A-50-140129. No. 3,706,561, isothiourea derivatives described in U.S. Pat.No. 3,706,561, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent No. 2,748,430, Japanese Patent Publication No. A polyamine compound described in JP-A-8836 can be used. Particularly, compounds having a mercapto group or a disulfide bond described in the above publication are preferable.

In addition, the bleaching solution or bleach-fixing solution of the present invention may contain bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, iodide). Ammonium). If necessary, pH of boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
One or more kinds of inorganic acids and organic acids having a buffering ability and alkali metal or ammonium salts thereof or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Water-soluble silver halide dissolving agents such as thioether compounds such as ethylenebisthioglycolic acid and 3,6-dithia-1,8-octanediol and thioureas, and these may be used alone or in combination of two or more. Can be used. Further, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-51-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of the fixing agent per one is preferably 0.3 to 2 mol, and particularly in the processing of a color photographic light-sensitive material for photography, 0.8 to 1.5 mol.
In the processing of a color photographic light-sensitive material for printing, the range is 0.5 to 1 mole.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is from 3 to
10 is preferable, and 5 to 9 is particularly preferable.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and the fixing solution of the present invention may contain, as a preservative, a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite,
) And metabisulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 0.50 mol / in terms of sulfite ion, more preferably 0.04 to 0.50 mol / mol.
~ 0.40 mol /.

As a preservative, the addition of sulfite is common,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, a fluorescent brightener, a chelating agent, a fungicide and the like may be added as required.

Next, among the magenta couplers of the present invention, the coupler of the general formula (I) will first be described in detail.

The compound of the general formula (I) used in the present invention is described in
These are already known in JP-A-53-34044, JP-A-55-62454 and JP-A-57-35858.

Preferred R ₂ in formula (I) is a hydrogen atom, an aliphatic acyl group or an aliphatic sulfonyl group, and particularly preferred R ₂ is a hydrogen atom.

It is known in the art that when R ₂ is a hydrogen atom, it has the following keto-enol form tautomerism. Thus, the structure on the left is equivalent to the structure on the right.

X ₁ is of a type capable of leaving at any of a sulfur, oxygen and nitrogen atom, and a sulfur atom leaving group is particularly preferred.

When X ₁ is a sulfur atom leaving group, the group bonded to the sulfur atom is an alkyl group, an aryl group or a heterocyclic group, and the alkyl group is a linear or branched alkyl group having 1 to 42 carbon atoms, an alkenyl group. A cycloalkyl group, an aralkyl group or an alkynyl group, which is a halogen atom, a hydroxy, a mercapto group, a cyano group, a nitro group,
Carboxyl group, aryl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, silyloxy group, carbamoyloxy group, phosphate oxy group, acylamino group, sulfonamide group An alkoxycarbonylamino group, an aryloxycarbonylamino group, a diacylamino group, a carbamoylamino group,
Sulfamoylamino group, pyrazolyl, imidazolyl,
Aromatic heterocyclic group such as triazolyl, piperidino group, non-aromatic heterocyclic group such as morpholino group, imide group, pyridone, monooxo nitrogen heterocyclic group such as sutcharin, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, A carbamoyl group, a sulfamoyl group, a silyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonyl group, an anilino group, and the like may be substituted.

Here, the aryl group is a phenyl group or a naphthyl group having 6 to 46 carbon atoms, which may be substituted by the substituent described for the substituent of the alkyl group in addition to the alkyl group.

Further, the heterocyclic group is a 5- to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom and a sulfur atom alone or simultaneously, and may be condensed with a benzene ring. Representative heterocyclic skeletons include the following.

In the formula, R ₅ represents a hydrogen atom, an alkyl group, or the same substituent (a group which may be substituted when X ₁ is an alkyl group) as described above for the substituent of the alkyl group, and R ₆ represents Represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.

The phenyl group represented by R ₁ may be substituted, and examples of the substituent include the substituents described above for the alkyl group of X ₁ in addition to the alkyl group.

The phenyl group represented by R ₃ may be substituted, and preferably may be substituted with at least one or more halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, or cyano groups.

It should be noted that R ₁ and R ₃ may be the same or different.

Particularly preferred magenta couplers represented by formula (I) are represented by formulas (III) and (IV).

General formula (III) General formula (IV) In the formula, Ar represents at least one or more halogen atoms, an alkyl group, alkoxy group, alkoxycarbonyl group or phenyl group which cyano group is substituted,, Z represents a halogen atom or an alkoxy group,, R ₇ is hydrogen Atom, halogen atom, alkyl group, alkoxy group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, diacylamino group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group,
An alkanesulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, an alkyloxycarbonylamino group, a ureido group, an acyl group, a nitro group, or a carboxy group, and R ₈ is a halogen atom, a hydroxy group, an amino group, an alkyl group Represents an alkoxy group, an aryloxy group or an aryl group, and R ₉ represents a hydrogen atom, an amino group, an acylamino group, an ureido group, an alkoxycarbonylamino group, an imide group, a sulfonamide group, a sulfamoylamino group, a nitro group, an alkoxy group. Carbonyl group,
A carbamoyl group, an acyl group, a cyano group, an alkylthio group, R ₁₀ represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group, and at least one of R ₈ and R ₁₀ is an alkoxy group; Represents a group, m represents an integer of 1 to 3, n represents an integer of 1 to 4, and 1 represents an integer of 1 to 3.

R ₁₁ represents an alkyl group or an aryl group;
₁₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an aryl group;
Represents an integer of 1 to 5, respectively.

More specifically, Ar is a substituted phenyl group. As the substituent, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 22 carbon atoms (eg, a methyl group, an ethyl group) Group, tetradecyl group,
a C-C22 alkoxy group (e.g., methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.), a C2-C23 alkoxycarbonyl group (e.g., methoxycarbonyl group, Such as an ethoxycarbonyl group and a tetradecyloxycarbonyl group) or a cyano group.

More specifically, Z is a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, etc.),
Or an alkoxy group having 1 to 22 carbon atoms (for example, a methoxy group, an octyloxy group, a dodecyloxy group, etc.).

If Re More particularly mentioned for R _7, R ₇ is a hydrogen atom, a halogen atom (e.g. a chlorine atom, a bromine atom, etc. fluorine atom), an alkyl group (e.g. methyl, t-Butaru group, 2
-Methanesulfonamidoethyl group, t-butanesulfonylethyl group, tetradecyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (for example, acetamido group, Benzamide group, butanamide group, tetradecaneamide group, α- (2,4-di-tert-
Amylphenoxy) acetamide group, α- (2,4-di-t
ert-amylphenoxy) butyramide group, α- (3-
Pentadecylphenoxy) hexanamide group, α- (4
-Hydroxy-3-tert-butylphenoxy) tetradecaneamide group, 2-oxo-pyrrolidin-1-yl group,
2-oxo-5-tetradecylpyrrolidin-1-yl group, N-methyl-tetradecaneamide, α- (3-methanesulfonamidophenoxy) tetradecaneamide group,
), Sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octanesulfonamide group, p-dodecylbenzenesulfonamide group, N-methyl-tetradecanesulfonamide group, etc.) , A sulfamoyl group (for example, N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N- [3- (dodecyloxy) -propyl] sulfamoyl group, N- [4- (2,4-di- tert
-Amylphenoxy) butyl] sulfamoyl group, N-
Methyl-N-tetradecylsulfamoyl group, etc.),
Carbamoyl group (for example, N-methylcarbamoyl group,
N-octadecylcarbamoyl group, N- [4- (2,4-
Di-tert-amylphenoxy) butyl] carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc., diacylamino group (N-succinimide group, N-
Phthalimide group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1-hydantoinyl group, 3- (N-acetyl-N-dodecylamino) succinimide group, etc.), alkoxycarbonyl group (For example, methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (for example, methoxysulfonyl group,
Octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (eg, phenoxysulfonyl group, 2,4-di-tert-amylphenoxysulfonyl group, etc.), alkanesulfonyl group (eg, Methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (for example,
Benzenesulfonyl group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (for example, ethylthio group,
Hexylthio group, benzylthio group, tetradecylthio group, 2- (2,4-di-tert-amylphenoxy) ethylthio group, etc., arylthio group (for example, phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino Groups (e.g., ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), ureido groups (e.g., N-methylureido group, N-phenylureido group, N, N-dimethylureido group, N-methyl-N-dodecylureido group, N-hexadecylureido group, N, N-
Dioctadecyl ureide group, etc.), acyl group (eg, acetyl group, benzoyl group, octadecanoyl group,
p-dodecaneamidobenzoyl group, etc.), nitro group,
Or a carboxy group. However, among the above substituents, those defined as alkyl groups have 1 to 42 carbon atoms, and those defined as aryl groups have 6 to 46 carbon atoms.

Stated in more detail R _8, R ₈ is a halogen atom (e.g., chlorine atom, bromine atom, etc.), hydroxy group, an amino group (a substituted or unsubstituted amino group, N- alkylamino, N, N -Dialkylamino group, N-aniline group, N
-Alkyl-N-arylamino group, represents a heterocyclic amino group, for example, N-butylamino group, N, N-dibutylamino group, N, N-dihexylamino group, N-piperidino group, N, N-bis (2-dodecyloxyethyl) amino group, N-cyclohexylamino group, N-phenylamino group, N, N-bis (2-hexanesulfonylethyl) amino group, etc.), alkyl group (linear or branched alkyl group) ,
Represents an aralkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, for example, a methyl group, a butyl group, an octyl group, a dodecyloxy group, a benzyl group, a cyclopentyl group, a 2-methanesulfonylethyl group, a 3-phenoxypropyl Group, etc.), alkoxy group (for example, methoxy group, butoxy group, benzyloxy group, 2-ethylhexyloxy group, dodecyloxy group, 2-methanesulfonylethyl group, 2-butanesulfonylethyl group, isopropyloxy group, 2- Chloroethyl group, 3- (2,4-
Di-tert-amylphenoxy) propyl group, 2- (N-
Methylcarbamoyl) ethoxy group, cyclopentyloxy group, 2-ethoxytetradecyloxy group, 4,4,4,3,3,
2,2-heptafluorobutyloxy group, 3- (N-butylcarbamoyl) propyloxy group, 3- (N, N-dimethylcarbamoyl) propyloxy group, 4-methanesulfonylbutoxy group, 2-ethanesulfonamidoethyl group , Etc.), an aryloxy group (for example, a phenoxy group,
A 2,4-dichlorophenoxy group or the like) or an aryl group (a substituted or unsubstituted phenyl group having 6 to 38 carbon atoms, a naphthyl group, for example, a phenyl group, an α- or β-naphthyl group, A chlorophenyl group, a 4-t-butylphenyl group, a methanesulfonamidophenyl group, a 2,4-dimethylphenyl group, etc., R ₉ is a hydrogen atom, an amino group (substituted or unsubstituted amino group and N-alkylamino Group, N, N-
Dialkylamino group, N-anilino group, N-alkyl-
Represents an N-arylamino group or a heterocyclic amino group, such as N-butylamino group, N, N-diethylamino group, N
-[2- (2,4-di-tert-amylphenoxy) ethyl] amino group, N, N-dibutylamino group, N-piperidino group, N, N-bis- (2-dodecyloxyethyl) amino group, N -Cyclohexylamino group, N, N-di-hexylamino group, N-phenylamino group, 2,4-di-tert-
Amylphenylamino group, N- (2-chloro-5-tetradecanamidophenyl) amino group, N-methyl-N-
Phenylamino group, N- (2-pyridyl) amino group,
Etc.), an acylamino group (for example, an acetamido group, a benzamide group, a tetradecaneamide group, a (2,4-di-tert
-Amylphenoxy) acetamide group, 2-chloro-benzamide group, 3-pentadecylbenzamide group, 2-
(2-methanesulfonamidophenoxy) dodecaneamide group, 2- (2-chlorophenoxy) tetradecaneamide group, etc.), ureido group (for example, methylureido group,
A phenylureido group, a 4-cyanophenylureido group,
Etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, dodecyloxycarbonylamino group, 2-ethylhexyloxycarbonylamino group,
Imide group (eg, N-succinimide group, N-
Phthalimide group, N-hydantoinyl group, 5,5-dimethyl-2,4-dioxooxazol-3-yl group, N-
(3-octadecenyl) succinimide group, etc.), sulfonamide group (for example, methanesulfonamide group, octanesulfonamide group, benzenesulfonamide group, 4
-Chlorobenzenesulfonamide group, 4-dodecylbenzenesulfonamide group, N-methyl-N-benzenesulfonamide group, 4-dodecyloxybenzenesulfonamide group, hexadecanesulfonamide group, etc.), sulfamoylamino group (for example, N-octylsulfamoylamino group, N, N-dipropylsulfamoylamino group, N-ethyl-N-phenylsulfamoylamino group, N- (4-butyloxy) sulfamoylamino group, etc.) Nitro group, alkoxycarbonyl group (for example, methoxycarbonyl group, butoxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, etc.), carbamoyl group (for example, N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-phenylcarbamoyl group, N- [3 -(2,4-di-tert-amylethoxy) propyl] carbamoyl group, etc.), acyl group (eg, acetyl group, benzoyl group, hexanoyl group, 2-ethylhexanoyl group, 2-chlorobenzoyl group, etc.) ), Cyano group, alkylthio group (for example, dodecylthio group, 2-ethylhexylthio group, benzylthio group, 2-oxocyclohexylthio group, 2- (ethyltetradecanoate) thio group, 2- (dodecylhexanoate) thio Group, 3-phenoxypropylthio group, 2-
Dodecanesulfonylethylthio group, etc.), and R ₁₀
It is hydrogen atom, hydroxy group, or a similar alkyl group as mentioned in R _8, an alkoxy group, an aryl group, R _8, R
_At least one of the ₁₀ represents an alkoxy group.

R ₁₁ represents the same alkyl group or aryl group as described for R ₈ , and R ₁₂ represents a hydrogen atom or the same halogen atom, alkyl group, alkoxy group or aryl group as described for R ₈ .

Next, the coupler of formula (II) will be described in detail.

X ₂ has the same meaning as the leaving group represented by X ₁ . R ₀ includes a hydrogen atom, an alkyl group, and a group which may be substituted when X ₁ is an alkyl group. When Za-Zb is a carbon-carbon double bond, it includes the case where it is a part of an aromatic ring. Also R ₄ or X ₂
To form a multimer of two or more. When Za or Zb is a substituted methine,
It also includes the case where a multimer is formed. However, if Za or Zb , At least one of R ₄ or R ₀ is Za, Zb
Both = If a N-R ₄ are, one at least of the hydrogen atoms of the methylene group directly linked to the backbone, but represents a group substituted, yet at least one -NHSO to R ₄ or R _0
It is preferable to include a ₂ -substituent.

In the general formula (II), the term "multimer" means a compound having two or more groups represented by the general formula (II) in one molecule, and includes a bis-isomer and a polymer coupler.
Here, the polymer coupler may be a homopolymer composed of only a monomer having a moiety represented by the general formula (II) (preferably having a vinyl group, hereinafter referred to as a vinyl monomer), or an aromatic primary amine developer. A copolymer may be made with a non-chromogenic styrenic monomer that does not couple with the oxidation product of

The compound represented by formula (II) is a 5-membered-5-membered condensed nitrogen heterocyclic coupler whose color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and is generally referred to as azapentalene. It has a structure. Preferred compounds among the couplers represented by the general formula (II) are represented by the following general formulas (V), (VI), (VII), (VIII) and (IX). VI
I).

Substituents R ₁₂ , R ₁₃ and R _{14 in the} general formulas (V) to (IX)
Represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group A carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, Represents an aryloxycarbonyl group.

R ₁₂ , R ₁₃ , R ₁₄ or X ₂ may be a divalent group to form a bis form. In addition, the general formulas (V) to (IX)
When the moiety represented by is in the vinyl monomer, R
₁₂ , R ₁₃ or R ₁₄ represents a mere bond or linking group,
Through this, the portions represented by the general formulas (V) to (IX) are bonded to the vinyl group.

More specifically, R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, a propyl group, a t-butyl group,
Trifluoromethyl group, tridecyl group, 3- (2,4-di-t-amylphenoxy) propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, Benzyl group, etc.), aryl group (for example, phenyl group, 4-t-
Butylphenyl group, 2,4-di-t-amylphenyl group,
4-tetradecanamidophenyl group, etc.), heterocyclic group (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group,
Alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2
-Methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-methylphenoxy group,
4-t-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-benzimidazolyloxy group, etc.), acyloxy group (eg, acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (eg, N
-Phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, etc.), acylamino group (eg, acetamido group) , Benzamide group, tetradecaneamide group, α- (2,4-di-t-amylphenoxy) butylamide group, γ- (3-t-butyl-4-hydroxyphenoxy) butylamide group, α- {4- (4 −
Hydroxyphenylsulfonyl) phenoxydidecamide group, etc.), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group) , N-acetylanilino group, 2
-Chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecaneamide} anilino group, etc., ureido group (for example, phenylureido group, methylureido group, N, N-dibutylureido group) ), Imide group (for example, N-succinimide group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group, etc.), sulfamoylamino group (for example, N,
N-dipropylsulfamoylamino group, N-methyl-
N-decylsulfamoylamino group, etc.), alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4 -T-butylphenoxy) propylthio group, etc.), arylthio group (for example,
Phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic thio group (Eg, 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group) , 2,4-di-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfone) Amide group, 2-methyloxy-5-t-butylbenze Carbamoyl group (eg, N-ethylcarbamoyl group, N,
N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-tert-amylphenoxy) propyl} carbamoyl group, etc. ), Acyl groups (eg, acetyl group, (2,4-di-tert-amylphenoxy) acetyl group, benzoyl group, etc.), sulfamoyl groups (eg, N-ethylsulfamoyl group, N, N
-Dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc., sulfonyl group (for example, Methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (for example,
Octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxy Carbonyl group (for example,
X represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, or the like), a carboxyl group, or an oxygen atom. Groups (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy,
Ethoxy oxaloyloxy group, pyrvinyloxy group,
Cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group,
-Methanesulfonylphenoxy group, α-naphthoxy group,
3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group ,
2-benzothiazolyloxy group, etc.), a group linked by a nitrogen atom (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4,5,6- Pentafluorobenzamide group,
Octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl- Ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-3 (2H) -oxo-
1,2-benzoisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl,
5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl- 5-hexadecyloxy-
3-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-piparoylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.), sulfur atom (For example, a phenylthio group, a 2-carboxyphenylthio group,
2-methoxy-5-t-octylphenylthio group, 4-
Methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert
-Octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group,
2-benzothiazolylthio group, 2-dodecylthio-5-
A thiophenylthio group, 2-phenyl-3-dodecyl-1,
2,4-triazole-5-thio group, etc.).

When R ₁₂ , R ₁₃ , R ₁₄ or X ₂ is a divalent group to form a bis-form, the divalent group may be further described in detail as follows:
Substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, 1,10-decylene group, -CH ₂ CH ₂ -O-CH
₂ CH ₂ —, etc.), a substituted or unsubstituted phenylene group (for example, 1,4-phenylene group, 1,3-phenylene group, —NHCO—R ₂ —CONH— group (R ₂ represents a substituted or unsubstituted alkylene group or a phenylene group.

When those represented by the general formulas (V) to (IX) are present in the vinyl monomer, the linking group represented by R ₁₂ , R ₁₃ or R ₁₄ is an alkylene group (substituted or unsubstituted alkylene group). For example, methylene group, ethylene group, 1,10-decylene group, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.), phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group) , 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, Etc.) are included.

The vinyl group in the vinyl monomer is represented by the general formula (V)
(IX) also includes those having a substituent other than those represented by (IX). Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid is a non-color-forming ethylene-like monomer that does not couple with the oxidation product of an aromatic primary amine developer.
α-chloroacrylic acid, α-alkacrylic acid (for example,
Methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n -Butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibisacrylamide, vinyl Esters (eg, vinyl acetate, vinyl propionate and vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, , Vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-2-
Pyrrolidone, N-vinylpyridine, and 2- and 4
-Vinyl pyridine and the like. The case where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together is also included.

JP-A-58-42045, Japanese Patent Application Nos. 58-88940, 58-52923,
The high-color-forming ballast groups described in JP-A-58-52924 and JP-A-58-52927 are applied to any of the compounds of the above general formulas (V) to (IX).

Specific examples of the magenta coupler used in the present invention are shown below, but are not limited thereto.

The magenta coupler represented by the general formula [I] is disclosed in
49-74027, 49-74028, JP-B-48-27930, 5
It is synthesized by the method described in 3-33846 and U.S. Pat. No. 3,519,429.

The magenta couplers represented by the general formula [II] are synthesized by the methods described in JP-A-59-162548, U.S. Pat. No. 3,725,067, JP-A-59-171956 and JP-A-60-33552, respectively. .

In the light-sensitive material of the present invention, functional materials such as colored couplers, DIR couplers, diffusible dye-forming couplers, and DIR hydroquinone can be used in addition to the above couplers.

The coupler of the present invention can be added to the light-sensitive material in any amount.
It is used in the range of 10 moles, preferably in the range of 0.1 mole to 1 mole, and most preferably in the range of 0.2 mole to 0.5 mole.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. In addition, the process of the latex dispersion method,
Specific examples of effects and latexes for impregnation are described in U.S. Pat.
No. 9,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Examples of the photosensitive material used in the present invention include color paper and color negative film.

First, for color paper, the silver bromide content is 10 mol%.
The above silver chlorobromide is used. Further, in order to obtain an emulsion having sufficient sensitivity without increasing fog, the silver bromide content is 20%.
It is preferably at least mol%, but when rapidity is particularly required, it may be at most 10 mol% or at most 5 mol%. In particular, an emulsion close to 1 mol% or less of pure silver chloride is preferable because rapid development is possible.

In the photographic emulsion layer of the color negative film used in the present invention, any of silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride may be used.
Preferred silver halides contain 30 mol% or less of silver iodide,
Silver iodobromide or silver iodochlorobromide. Particularly preferred is silver iodobromide containing from 2 mol% to 25 mol% of silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular particles having regular crystals such as tetradecahedron and rhombic dodecahedron may be used, or may have irregular crystal forms such as spheres, or have crystal defects such as twin planes, or A composite form thereof may be used.

Further, tabular grains may be used, and when this is used, improvement in sensitivity including improvement in color sensitization efficiency, improvement in the relationship between sensitivity and granularity,
It is possible to achieve an improvement in the sharpness, an improvement in the development progress, an improvement in the covering power, an improvement in the crossover, and the like.

Here, the tabular silver halide grains have a diameter / thickness ratio of 5 or more, for example, 8 to 20 or 5 or more and 8 or less.

Monodisperse emulsions can also be used as the emulsion, and silver halide grains having an average grain diameter of more than about 0.1 micron, at least about 95% by weight of which are within ± 40% of the average grain diameter.
% Are typical. Emulsions having an average grain diameter of about 0.25 to 2 microns and having at least about 95% by weight or at least about 95% by number of silver halide grains within the average grain diameter ± 20% can be used in the present invention. .

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, heminanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

The sensitizing dye used in the present invention includes RESEARCH DI
SCLOSURE Volume 176, Item17643 IV, p.23 (December 1978)
Can be mentioned.

Here, the sensitizing dye can be used in any step of the production process of the photographic emulsion and can be used in any stage immediately after the production and immediately before coating. Examples of the former include a silver halide grain forming step, a physical ripening step, and a chemical ripening step.

Particularly in U.S. Pat.Nos. 4,183,756 and 4,225,666,
Addition of a spectral sensitizing dye to the emulsion after the formation of stable nuclei for silver halide grain formation has advantages such as increased photographic sensitivity and enhanced adsorption of the spectral sensitizing dye by silver halide grains. It has been disclosed.

The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; Azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes, pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonate, benzenesulfonate, benzenesulfonate and the like Can be added.

In order to correct unnecessary absorption in the short wavelength region of the dye formed from the magenta and cyan couplers, it is preferable to use a colored coupler in combination with the color negative photosensitive material for photography. U.S. Pat.No.4,163,670 and JP-B-57-39413
Typical examples thereof include a yellow-colored magenta coupler described in U.S. Pat. No. 4,049,849 and a magenta-colored cyan coupler described in U.S. Pat. Nos. 4,004,929, 4,138,258 and British Patent 1,146,368.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blurred couplers are disclosed in U.S. Pat.No. 4,366,237 and British Patent 2,125,5.
No. 70 has a specific example of a magenta coupler, and EP 9
No. 6,570 and German Offenlegungsschrift 3,234,533 describe specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211. Specific examples of the polymerized magenta coupler, UK Patent No. 2,102,173,
U.S. Pat.No. 4,367,282, Japanese Patent Application Nos. 60-75041 and 60
-113596.

Various couplers can be used in combination of two or more in the same layer of the photosensitive layer, or the same compound can be introduced in two or more different layers in order to satisfy the characteristics required for the photosensitive material. it can.

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide,
Preferably 0.01 to 0.5 mol for a yellow coupler,
In the case of a cyan coupler, the amount is 0.002 to 0.3 mol.

The present invention may include a coupler which releases a development inhibitor during development, a so-called DIR coupler.

Examples of the DIR coupler include those which release a heterocyclic mercapto-based development inhibitor described in, for example, US Pat. No. 3,227,554; and those which release a benzotriazole derivative as a development inhibitor described in JP-B-58-9942; Kuniaki 51-16
No. 141, etc., so-called non-colored DIR couplers;
No.-90932, which releases a nitrogen-containing heterocyclic development inhibitor accompanied by decomposition of methylol after leaving; US Pat.
Nos. 4,248,962 and JP-A-57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction after elimination; JP-A-56-114945, JP-A-57-15423, and JP-A-57-188035. ,
No. 58-98728, No. 58-209736, No. 58-209737, No. 5
Nos. 8-209738, 58-209739, and 58-209740, which release a development inhibitor by electron transfer through a conjugated system after leaving; Japanese Patent Application Laid-Open Nos. 57-151944 and 58-209740.
No. 2,179,32 which release a diffusible development inhibitor which deactivates the development inhibiting ability in the present solution;
No. 9-39653, which release a reactive compound and generate a development inhibitor by in-film reaction during development or deactivate the development inhibitor.
Among the DIR couplers described above, those which are more preferable in combination with the present invention are a developer inactivated type represented by JP-A-57-151944; US Pat. No. 4,248,962 and JP-A-57-151944.
Timing type represented by −154234; Japanese Patent Application No. 59-3965
The reaction types represented by No. 3 are particularly preferable. Among them, JP-A-57-151944, JP-A-58-217932, JP-A-59-75474, JP-A-59-82214 and JP-A-59-82214 are particularly preferable. And DIR couplers described in Japanese Patent Application No. 59-39653.

As the light-sensitive material that can be used in the present invention, a compound that releases a nucleating agent or a development accelerator or a precursor thereof (hereinafter, referred to as a “development accelerator”) imagewise during development can be used. . Typical examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188, and include a development inhibitor and the like by a coupling reaction with an oxidized aromatic primary amine developer. , Ie, DAR couplers.

It is preferable that the development accelerator and the like released from the DAR coupler have an adsorptive group to silver halide. Specific examples of such a DAR coupler are described in JP-A-59-157638 and JP-A-59-170840. No. A DAR which forms an N-acyl-substituted hydrazine having a monocyclic or condensed heterocyclic ring as an adsorptive group, which is released from a coupling active position of a photographic coupler with a sulfur atom or a nitrogen atom.
Couplers are particularly preferred, and specific examples of such couplers are described in Japanese Patent Application No. 58-237101.

JP-A-60-37556, which has a development accelerator moiety in the coupler residue, or JP-A-58-214808, which releases a development accelerator by an oxidation-reduction reaction with a developing agent. Can also be used in the light-sensitive material of the present invention.

The DAR coupler is preferably introduced into the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention.
As described in JP-A-172640 or Japanese Patent Application No. 58-237104, it is preferred to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers.

The light-sensitive material prepared by using the present invention may be a color fogging inhibitor or a color mixture inhibitor, such as a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, and a sulfonamide phenol. A derivative or the like may be contained.

The light-sensitive material that can be used in the present invention may include a known anti-fading agent. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-
Hindered phenols, mainly hydroxycoumarans, spirochromans, p-alkoxyphenols, bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenols of these compounds Representative examples thereof include ether or ester derivatives obtained by silylating or alkylating a hydroxyl group. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

In the photosensitive material that can be used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, benzotriazoles, butadienes, cinnamates, benzophenones, and high molecular compounds having an ultraviolet absorbing residue can be used. Also, a fluorescent whitening agent that absorbs ultraviolet light may be used. Typical examples of ultraviolet absorbers are described in RD24239 (June 1984) and the like.

The light-sensitive material which can be used in the present invention comprises one or more interfaces for various purposes such as coating aid, antistatic, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (for example, development acceleration, high contrast, sensitization). An active agent may be included.

The light-sensitive material that can be used in the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye, or for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used. In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

As the binder or protective colloid used for the photosensitive material, gelatin is advantageously used, but a hydrophilic synthetic polymer or the like can also be used. As gelatin, lime-processed gelatin, acid-processed gelatin, derivative gelatin, and the like can also be used. Specifically, Research Disclosure No. 17
Volume 6, No. 17643 (December 1978), section IX.

In the photosensitive material that can be used in the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the back layer. Specific examples thereof include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-
Hydroxy-1,3,5-triazine, etc. and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bisvinylsulfonylacetamidoethane or vinyl polymers having a vinylsulfonyl group in the side chain) ) Is preferred because it quickly cures hydrophilic colloids such as gelatin and provides stable photographic properties. N-carbamoylpyridinium salts and haloamidinium salts are also fast and excellent in curing speed.

Regarding the above-mentioned additives and the like, see RESEARCH DISCLOSURE, Vol. 176, No. 1764
3 (December 1978), p.22 to p.28, can be used.

The film is applied to a rigid support such as a plastic support or a plastic support (such as cellulose nitrate, cellulose acetate, polyethylene terephthalate) or paper which is generally used for a color light-sensitive material used in the present invention, or a glass. . See RESE for details on the support and coating method.
ARCH DISCLOSURE Volume 176, Item 17643, Item XV (p. 27), Item XVII (p. 28) (December 1978).

(Example) Hereinafter, an example of the present invention will be described.

Example 1 A multilayer color printing paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) In 4.4 g, 27.2 cc of ethyl acetate and a solvent (Solv-
1) 7.7 cc was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (silver bromide 8
(0.0 mol%, containing 70 g / kg of Ag) was added with the following blue-sensitive sensitizing dye at 5.0 × 10 ⁻⁴ mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(5.0 × 10 ^-4 mol per mol of silver halide) (4.0 × 10 ^-4 mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer at 2.6 × 10 ⁻³ mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer per mole of silver halide.
4.0 × 10 ^-6 mol, 3.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 × 10
^-2 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers indicate the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue sensitive layer) Silver halide emulsion (Br: 80%) 0.26 Gelatin 1.83 Yellow coupler (ExY) 0.83 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion (Br: 80%) 0.16 Gelatin 1.79 Magenta coupler (ExM) 0.32 Color image stabilizer (Cpd-3) 0.20 Color image stabilizer (Cpd-4) 0.01 Color image stabilizer (Cpd-8) 0.03 colors Image stabilizer (Cpd-9) 0.03 Solvent (Solv-2) 0.65 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.62 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red-sensitive layer) Silver halide emulsion (Br: 70%) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.34 Color image stabilizer (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) 0.23 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing agent (UV-1) 0.21 Solvent (Solv-3) 0.08 7th layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification
17%) 0.17 Liquid paraffin 0.03 The following emulsions were used for each layer.

After imagewise exposure of the above sample, each of the washing waters was subjected to running processing in the following processing steps. The treatment was carried out for 10.5 m ² each day for 15 consecutive days. Incidentally, bring amount of light-sensitive material of the washing water was found to be light-sensitive material 1 m ² per 30 ml.

Color developer Bleaching fixer Rinse water Well water having the following quality (rinse water A) and H-type strongly acidic cation exchange resin (manufactured by Mitsubishi Chemical Corporation, Diaion SK-
1B) and OH-type strong basic anion exchange resin (Mitsubishi Kasei Corporation)
Through a column packed with Diaion SA-10A). (Washing water B) Running treatment was carried out using washing water prepared by adding calcium chloride and magnesium chloride to the washing water B to adjust the calcium and magnesium concentrations shown in Table 1. After the completion of the running process, the photosensitive material was exposed to a wedge and processed. A light fastness test was performed by irradiating the processed photosensitive material with a xenon fade meter (85,000 Lux) for 200 hours.

As a measure of light fastness, a magenta color density of 2.0 before the light fastness test was indicated by a percentage of the density reached after the light fastness test and an increase in the yellow density of the unexposed portion.

The appearance of turbidity, suspended matter, mold, etc. in each final washing bath was visually observed.

 Table 1 shows the obtained results.

As can be seen from Table 1, if the treatment is carried out using washing water in which calcium and magnesium are reduced, the light resistance of the photosensitive material after the treatment is greatly improved and the stability of the washing water is remarkably improved.

Further, the following stabilizing solutions A and B were prepared using washing water A and washing water B in place of the washing water, and the running treatment and the light resistance test were carried out in the same manner as above. The prepared stable liquid B using water B was superior to the stable liquid A.

Stabilizer mother liquor (common to replenisher) 1-hydroxyethylidene-1,1'-diphosphonic acid (60%) 1.6 ml bismuth chloride 0.35 g ammonium chloride 2.0 g polyvinylpyrrolidone 0.25 g aqueous ammonia 2.5 ml o-hydroxybiphenyl 0.15 g optical image brightening agent (4,4'-Zia Minosuchiruben system) by adding 1.0 g water (washing water a Moshiku the utilization B) 1000 ml pH 7.5 pH is adjusted with aqueous ammonia or hydrochloric acid.

Example 2 Example 2 was repeated except that the photosensitive material prepared in Example 1 was washed with water.
A running process and a light resistance test were performed in the same manner as in Example 1.

The tests were performed under the same conditions for both the following washing water C and washing water D, and comparisons were made. The replenishing amount and washing time of the washing water were set as shown in Table-2.

(Washing water C) One tablet for sterilization described below was dissolved per 10 tap water. (Contains 31 ppm of Ca and 8 ppm of Mg) (Washing water D) Tap water is passed through an ion exchange device having a resin capacity of 3 and a resin cartridge with a bet length of 30 cm at a rate of 500 ml / min. Was dissolved at a rate of 1 tablet per 10 ion-exchanged water.
(Containing 0.8 ppm of Ca and 0.4 ppm of Mg) The ion exchange resin used was Amberlite MB-2 manufactured by Organo Corporation.

(Preparation of tablets for sterilization) 1.3 g of sodium sulfate and 0.2 g of dichlorinated sodium isocyanurate are mixed, and a pressure of 80 kg / cm ² is applied thereto to obtain a diameter of 13 m / m.
Into a tablet.

Table 2 shows the washing conditions and the light resistance test results of each treatment.

As described above, the effect of the present invention becomes more remarkable as the replenishing amount of the washing water is smaller and the washing time is shorter.

Example-3 The magenta coupler (M-7 described in the text) used in the light-sensitive material prepared in Example-1 was used for M-5 and M-1.
7. A sample was prepared in which M-35, M-36, M-47 and M-72 were replaced, and a similar test was performed under the conditions of process No. 2 of Example 2 to obtain similar results. Was done.

Example 4 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) In 4.4 g, 27.2 cc of ethyl acetate and a solvent (Solv-
1) 7.7 cc was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. Meanwhile, silver chlorobromide emulsion (silver bromide
0.7 mol%, containing 70 g / kg of Ag) and 5.0 × 10 ⁻⁴ mol of the following blue-sensitive sensitizing dye per mol of silver was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dyes in each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

The following emulsions were used for each layer.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue sensitive layer) Silver halide emulsion (Br 0.7 mol%) 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-2) 0.08 Third layer (green sensitive layer) ) Silver halide emulsion (Br 0.4 mol%) 0.16 Gelatin 1.80 Magenta coupler (ExM) 0.39 Color image stabilizer (Cpd-3) 0.24 Color image stabilizer (Cpd-8) 0.013 Color image stabilizer (Cpd-9) 0.019 Solvent (Solv-3) 0.52 Solvent (Solv-4) 0.26 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.62 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red-sensitive layer) Silver halide emulsion (Br0.1 mol%) 0.23 Gelatin 1.49 Cyan coupler ( ExC) 0.47 Color image stabilizer (Cpd-6) 0.20 Polymer (Cpd-7) 0.28 Solvent (Solv-4) 0.28 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.21 Solvent (Solv- 3) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification
17%) 0.17 Liquid paraffin 0.03 (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ After imagewise exposure of the above light-sensitive material, using a paper processor, a running process was performed for 10.5 m ² each day for 15 days in the following processing steps.

However, a running treatment was performed using the washing water C or D of Example 2 as the washing water, and the two were compared.

The composition of each processing solution is as follows.

Bleach-fix solution (mother liquor and replenisher are the same) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Glacial acetic acid 9g Add water 1000ml pH (25 ° C) 5.40 After running, the sample was exposed to a wedge.
The same light fastness test was performed. The results are as follows, and an image having excellent light fastness can be obtained by using the present invention.

Further, the same test as above was conducted by changing the formulation and replenishing amount of the bleach-fixing solution and the replenishing amount of the washing water as follows, and introducing the overflow solution of the washing water into the bleach-fixing bath. However, similar results were obtained.

Bleach-fixing replenisher water 200ml Ammonium thiosulfate (70%) was added to 500ml sodium sulfite 60g Ethylenediaminetetraacetic acid iron (III) ammonium 140g disodium ethylenediaminetetraacetate 30g water 1000 ml pH with (25 ° C.) 6.70 The replenishing amount (per photosensitive material 1 m ² Bleach-fix replenisher 100 ml Rinse water 200 ml Example-5 A multilayer color photosensitive material having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene.

Layer E9 Protective layer Layer E8 UV absorbing layer Layer E7 Blue sensitive emulsion layer Layer E6 UV absorbing layer Layer E5 Yellow filter layer Layer E4 UV absorbing layer Layer E3 Green sensitive emulsion layer Layer E2 UV absorbing layer E1 layer Red-sensitive emulsion layer Support B1 layer Anti-curling layer B2 layer Protective layer An emulsion was prepared as follows.

A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were mixed with 0.5 g of 3,4-dimethyl-1,3-
It was added simultaneously to the aqueous solution of gelatin to which thiazoline-2-thione had been added at 55 ° C. for about 5 minutes with vigorous stirring to obtain a monodispersed emulsion having an average particle diameter of about 0.2 μm (silver bromide content: 40 mol%). A silver chlorobromide emulsion was obtained. Per mole of silver
35mg sodium thiosulfate and 20mg chloroauric acid (tetrahydrate)
And heated at 55 ° C. for 60 minutes to perform a chemical sensitization treatment.

The silver chlorobromide particles thus obtained were used as a core to further grow them by further treating in the same precipitation environment for 40 minutes, and finally a monodispersed core having an average particle diameter of 0.4 μm /
A shell chlorobromide emulsion was obtained. The coefficient of variation of the particle size is approximately
15%.

To this emulsion was added 3 mg of sodium thiosulfate and 3.5 mg of chloroauric acid (tetrahydrate) per mole of silver,
The mixture was heated for a minute to perform a chemical sensitization treatment to obtain an internal latent image type silver halide emulsion.

 The coating solution was prepared as follows.

Preparation of Coating Solution for Layer E1 40 cc of ethyl acetate and 7.7 cc of solvent (ExS-1) were added to 13.4 g of cyan coupler (ExCC-1), 5.7 g of color image stabilizer (ExSA-1) and 10.7 g of polymer (ExP-1). This solution was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a red-sensitive sensitizing dye shown below was added to the internal latent image type emulsion (containing 63 g / kg of Ag) in an amount of 2.5 × 10 ^-4 mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the E2 to E9 layers and the B1 and B2 layers were also prepared in the same manner as the E1 layer coating solution. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-
Triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

The following dyes were used as irradiation prevention dyes.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the amount applied per m ² . The silver halide emulsion and colloidal silver represent the coating weight in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] Layer E1 Silver halide emulsion 0.39 g Gelatin 1.35 g Cyan coupler (ExCC-1) 0.40 g Color image stabilizer (ExSA-1) 0.17 g Polymer (ExP-1) 0.32 g Solvent (ExS-1) 0.23 g Development regulator (ExGC-1) 32 mg Stabilizer (ExA-1) 5.8 mg nucleation accelerator (ExZS-1) 0.37 mg Nucleating agent (ExZK-1) 9.9 μg Layer E2 Gelatin 1.6 g Ultraviolet absorber (ExUV-1) 0.62 g Color mixing inhibitor (ExKB-1) 0.06 g Solvent (ExS-2) 0.24 g Layer E3 Silver halide emulsion 0.27 g Gelatin 1.79 g Magenta coupler (ExMC-1) 0.32 g Color image stabilizer (ExSA-2) 0.20 g Solvent (ExS-3) 0.65 g Development modifier (ExGC-1) 22 mg Stabilizer (ExA-1) 4 mg Nucleation accelerator (ExZS-1) 0.26 mg Nucleator (ExZK-1) 3.4 μg Layer E4 Gelatin 0.53 g Ultraviolet absorber (ExU V-1) 0.21 g Color mixture inhibitor (ExKB-2) 0.02 g Solvent (ExS-2) 0.08 g Layer E5 Colloidal silver 0.10 g Gelatin 0.53 g Ultraviolet absorber (ExUV-1) 0.21 g Color mixture inhibitor (ExKB-) 2) 0.02 g Solvent (ExS-2) 0.08 g E6 layer Same as E4 layer E7 layer Silver halide emulsion 0.26 g Gelatin 1.83 g Yellow coupler (ExYC-1) 0.83 g Color image stabilizer (ExSA-3) 0.19 g Solvent (ExS-4) 0.35 g Development modifier (ExGC-1) 32 mg Stabilizer (ExA-1) 2.9 mg Nucleation promoter (ExZS-1) 0.2 mg Nucleator (ExZK-1) 2.5 μg Layer E8 Seratin 0.53 g Ultraviolet absorber (UV-1) 0.21 g Solvent (Solv-3) 0.08 g Layer E9 Gelatin 1.33 g Acrylic modified copolymer of polyvinyl alcohol (degree of modification)
17%) 0.17g Liquid paraffin 0.03g Latex particles of polymethyl methacrylate (average particle size 2.8
μm) 0.05 Layer B1 Gelatin 8.7g Layer B2 Same as Layer E9 (ExS-2) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The above samples were exposed imagewise, and each of them was separately subjected to running processing in an automatic developing machine in the following processing steps. The replenishment amount, carry-in amount and processing amount by the photosensitive material were the same as those in Example-1. Processing time Temperature Color development 2 minutes 05 seconds 37 ° C Bleaching and fixing 40 seconds 37 ° C Rinse 30 seconds 37 ° C water rinse 30 seconds So-called countercurrent washing method.

pH was adjusted with potassium hydroxide or hydrochloric acid.

pH was adjusted with aqueous ammonia or hydrochloric acid.

As the washing water, the washing water A or the washing water B of Example 1 was used. After the running treatment, a light resistance test was performed in the same manner as in Example-1.

The results were the same as in Example 1, and a photographic image having excellent light fastness could be obtained by using the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideaki Naruse 210 Nakanuma, Minamiashigara Fuji Photo Film Co., Ltd. (56) References JP-A-60-220345 (JP, A) JP-A-60-241053 (JP) JP-A-61-43749 (JP, A) JP-A-61-151650 (JP, A) JP-A-61-251855 (JP, A) JP-A-61-273544 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide color light-sensitive material containing at least one magenta coupler represented by the following general formula (I) or (II), wherein the concentration of calcium and magnesium compounds is 5 mg / or less as calcium and magnesium, respectively. Unused washing replenisher and / or
Alternatively, a method for processing a silver halide color light-sensitive material, wherein the processing is performed while an unused stable replenisher is added to a washing bath and / or a stabilizing bath. General formula (I) General formula (II) (Wherein R ₁ and R ₃ represent a phenyl group, R ₂ represents a hydrogen atom, an aromatic acyl group or an aliphatic or aromatic sulfonyl group, R ₄ represents a hydrogen atom or a substituent, X ₁ , X ₂ represents a group capable of leaving during a coupling reaction with an oxidized form of the developing agent, and Za and Zb represent Or = N-. R ₀ represents a hydrogen atom or a substituent. )